CN1124897C - Method for preparing metal base nano oxide net - Google Patents
Method for preparing metal base nano oxide net Download PDFInfo
- Publication number
- CN1124897C CN1124897C CN 01126993 CN01126993A CN1124897C CN 1124897 C CN1124897 C CN 1124897C CN 01126993 CN01126993 CN 01126993 CN 01126993 A CN01126993 A CN 01126993A CN 1124897 C CN1124897 C CN 1124897C
- Authority
- CN
- China
- Prior art keywords
- oxide
- nano
- metal base
- preparing metal
- net according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Other Surface Treatments For Metallic Materials (AREA)
- Laminated Bodies (AREA)
- Catalysts (AREA)
Abstract
The present invention mainly relates to a method for using lamination layer nano assembling technology for preparing a metal base oxide net. In the method, a nano oxide glue solution is used as an adsorption deposition solution, and a metal net is used as a base material; under the action of electrostatic attraction, the lamination layer method is used for assembling a nano oxide on the metal net. A heterozygous metal base oxide net can also be obtained by alternately adsorbing various oxide colloids. An ultrathin oxide film on the prepared lattice surface can provide fast diffusion and a high active site utilization rate. The high heat transfer property of a metal base bottom is suitable for an exothermal reaction. A unique net structure is more superior in the aspect of mass transfer and is convenient for operation. The method can be used for catalyzing industry and separation industry, environmental protection, the preparation of sensors and the decoration of electrodes, and has the advantages of convenient operation, high speed, low requirement for devices, easy control of a deposition process and wide application perspective.
Description
Technical field
The present invention is a kind of method for preparing metal base nano oxide net with the layer laminate technology.
Background technology
Nano-oxide especially the semiconductor nano oxide owing to having the broad research interest that some unique advantages energy have caused people.The for example variation of the magnetic generation of magnetic material tri-iron tetroxide when nanoscale.Titanium dioxide with photocatalytic activity, zinc oxide has best activity at certain nanoscale, outstanding advantage is arranged in water body and gas purification, and for example phenols decomposition in the water body, chloride carcinogenic organic matter decompose freon decomposition, nitrogen-containing compound decomposition etc. in the gas.But the catalyst of preparation exists diffusion and the incomplete problem of illumination because particle is bigger usually, and the nanoscale conductor oxidate then shows better catalytic performance.But discrete nano-oxide is difficult to practical application again.If nano-oxide is assembled into network structure, can not only solves beaded catalyst diffusion and illumination problem, and can make full use of nano-oxide.Can also prepare air-sensitive or light sensor.In used carrier, wire netting is because cheap, be easy to make different shape and have high thermal conduction rate, have an enormous advantage, make oxide in the high catalytic activity of maintenance, can also provide less diffusional resistance than other substrate tool.
Summary of the invention
The objective of the invention is to find a kind of simple and easy to control, economic and assemble method of the nano material layer laminate Electrostatic Absorption of synthetic Metal Substrate oxide grid apace.
The preparation Metal Substrate zeolite involved in the present invention or the nanometer assemble method of oxide grid are as follows:
1. synthetic oxide colloid is dispersed in the colloidal oxide solution that forms various concentration and pH value in the aqueous solution;
2. preliminary treatment is carried out on the wire netting surface, method is that wire netting concentration was soaked 5 minutes～1 hour at 0.1～5% polycation electrolyte solution, clean 1～6 time with distilled water then, soaked 5 minutes～1 hour with 0.1～5% polyanion electrolyte solution again, clean 1～6 time with distilled water then, so circulate repeatedly (1～10 time) makes the wire netting surface be with electric charge;
3. the wire netting that the surface is charged soaks the regular hour in the oxide glue of variable concentrations, taking-up is with the solution washing of distilled water or certain pH value 1～10 time, alternately adsorb polyelectrolyte and oxide colloid then to desired thickness, after each layer or two layers of oxide colloid deposition with the Metal Substrate oxide net of gained uniform temperature airing 1～12 hour;
4. with the product roasting in the atmosphere of not corroding wire netting matrix that obtains, promptly obtain the oxide net of wire netting base;
Wherein in 1 said nano-oxide size in nanometer between the micrometer range, concentration is (wt%) between 0.05-20%, the pH value is between 1-14.
Polycation electrolyte and polyanion electrolyte can be respectively PDDA (PDDA) and poly-p-sulfonic acid base styrene (PSS) or the like in 2, can positively charged after the wire netting modification, and also can be electronegative.
Oxide colloid can be used surperficial positively charged in 3, also can be with electronegative oxide, and per deposition process time in step is 1 second to 20 hours, dries can at room temperature dry or heat and dry, 5～200 ℃ of airing temperature.
In 4 sintering temperature 200-1000 ℃.
Wire netting can be woven wires such as alloy, stainless steel as matrix, but optimum with stainless steel cloth, and price is not high, and is respond well.
Above-mentioned oxide coating on the wire netting that the layer laminate technology obtains dried be placed in nitrogen or other inert gas, as argon gas, helium etc., the intensification roasting, again in aerating oxygen or the air atmosphere 200-1000 ℃ of roasting, or directly aerating oxygen or air total roasting time 1-50 hour, obtain the Metal Substrate oxide net at same roasting temperature.
The present invention's implementation condition preferably is:
The oxide particle size is the 1-5000 nanometer.
The concentration of oxide particle is 0.1-10%.
The pH value of oxide solution is at 2-12.
Used polyelectrolyte is polycation electrolyte or polyanion electrolyte, as PDDA (PDDA), and poly-p-sulfonic acid base styrene (PSS).
Absorption deposition afterproduct dries at 5-200 ℃.
Drying temperature is 40-160 ℃
The sintering temperature of roasting process is 400-800 ℃, keeps 0-12 hour in not corroding wire netting matrix gas atmosphere such as nitrogen or inert gas atmosphere, keeps 1-8 hour in oxygen or the air atmosphere.
Better implement condition of the present invention is:
The size of the colloidal particle of oxide glue is the 1-200 nanometer.
It is 60-120 ℃ that product dries temperature.
This method can prepare the oxide net of various Metal Substrate, as the structure oxide nets such as titanium oxide, zinc oxide, iron oxide, zirconia, silica and aluminium oxide of copper mesh, steel mesh, nickel screen base.
The Metal Substrate oxide net that the inventive method obtains has the oxide coating and the conductive substrate of all even densifications, therefore can be used for the preparation of electrodes selective or sensor.
By preparing the product of the present invention that various types of oxides obtain, have a clear superiority at the like product than single oxide aspect catalyst, waste water and the exhaust-gas treatment.
Above-mentioned condition had both improved preparation efficiency, had guaranteed product quality and yield rate again.
The oxide net that method provided by the present invention obtains, has the time cycle weak point that produces finished product, surface mesh oxide skin(coating) even compact, the particle size of oxide are nanoscale and the characteristics that can control in advance, can also control the thickness of oxidation film by changing number of deposition cycles.Layer laminate method of the present invention is implemented convenient and simple, and is less demanding to instrument, and deposition process is easy to outside regulation and control.Be hopeful to be used to prepare at catalysis, separation industries and the composition metal base oxide net that in the modification of the preparation of sensor, electrode, has wide application prospects.
The specific embodiment
Example 1
The 10mL butyl titanate with the dilution of 50mL absolute ethyl alcohol, is got the 50mL deionized water with there-necked flask, then the butyl titanate dilution is added in the deionized water, drip speed control built in 1 per second.And vigorous stirring is to prevent the generation of inhomogeneous precipitation simultaneously, and the adding mass percent is 1% surfactant OP in stoste, behind the suction filtration sediment is washed 2-3 time with 30mL ethanol.Proper amount of deionized water is added in the sediment, disperseed 0.5 hour, obtain the TiO of certain density surperficial lotus positive electricity with ultrasonic wave
2Colloid (30nm).Earlier preliminary treatment is carried out on stainless steel steel wire surface before the deposition zeolite, method is to be that 0.5% polyanion electrolyte solution soaked 20 minutes with steel wire in concentration, clean 4 times with distilled water then, make stainless steel steel wire surface be with negative electrical charge, with the stainless steel steel wire of surperficial bear electricity TiO at surperficial lotus positive electricity
2Soaked 20 minutes in the colloid, take out with distilled water solution washing 4 times, room temperature is dried and is promptly obtained stainless steel-based nano-TiO
2Net sample A
1
Example 2-4
Carry out the layer laminate experiment by the method for example 1, but to the pretreated method difference of stainless steel steel wire.With soaking 20 minutes with 0.3% polycation electrolyte solution again after the PSS modification, clean 4 times with distilled water then, so use poly-cloudy (or sun) ionic electrolytes alternately to adsorb once, secondary, three times, and to make outermost layer be PSS, will be through once, secondary has made stainless steel-based nano-TiO after three polyelectrolyte circulation modifications
2Net is designated as A respectively
2, A
3, A
4
Example 5-7
Carry out the layer laminate experiment with the method identical with example 3, but to nano-TiO
2The mass percent concentration of colloidal solution carries out modulation, uses 0.1%, 0.5%, 6% nano-TiO respectively
2Glue; Obtained stainless steel-based nano-TiO
2Net is designated as A respectively
5, A
6, A
7
Example 8-9
Carry out the layer laminate experiment with the method identical, but use the TiO of different-grain diameter with example 6
2Colloid is a building block, is respectively the TiO of 6nm and 60nm with particle diameter
2Glue; Obtained the stainless steel nano-TiO
2Net is designated as A respectively
8, A
9
Example 10-13
Carry out the layer laminate experiment with the method identical with example 8, but to depositing Ti O
2The thickness of film is regulated and control, and alternately adsorbs polycation electrolyte and nano-TiO by changing
2The cycle-index of colloid obtains the TiO of different-thickness
2Film, through 3,7,15,30 times sorption cycle has obtained stainless steel-based TiO
2Net is designated as A respectively
10, A
11, A
12, A
13
Example 14
Carry out the layer laminate experiment with the method identical, but select the TiO of polycation electrolyte PDDA and surperficial bear electricity in the experimentation for use with example 11
2Nano particle (particle size 6nm); And when carrying out charged modification and handling, last one deck uses PDDA to stainless steel-based, makes the stainless steel steel wire surface lotus that becomes positively charged.Through 7 PDDA/TiO
2Sorption cycle has obtained stainless steel-based TiO
2Net is designated as A
14
Example 15-16
Carry out the layer laminate experiment with the method identical, but metal matrix becomes copper mesh or nickel screen, has obtained complete metallic copper or nickel base nanometer TiO with example 14
2Net is designated as A respectively
15And A
16
Example 17-19
Carry out the layer laminate experiment with the method identical with example 14, but deposit fluid becomes zinc oxide, tri-iron tetroxide or silicon oxide nanoparticle have obtained complete Metal Substrate oxide net, are designated as A respectively
17, A
18, A
19
Example 20
Carry out the layer laminate experiment with the method identical, but alternately change the type of employed nano zeolite, by silica and TiO with example 14
2Nano particle is absorption alternately, has obtained SiO
2/ TiO
2Composite stainless steel base zeolite net is designated as A
20
Example 21
With example 14 resulting sample A
14Roasting is warming up to 500 ℃ with 5 ℃/minute temperature programming speed, logical nitrogen 8 hours, and roasting 6 hours in oxygen atmosphere under the uniform temp is then removed organic molecule, the stainless steel-based nano-TiO that obtains
2Net is designated as B
1
Example 22
The stereoscan photograph of the said goods (SEM) all absorbs on Philips XL30 D6716 instrument, characterizes with XRD (carrying out on Rigaku D/Max-IIA type X-ray diffractometer).From electromicroscopic photograph as can be seen, the used layer laminate method of the present invention can be prepared oxidation film fast on woven wires such as stainless steel under more convenient condition, and this film is to be formed by build-up of particles one by one, and particle size remains unchanged substantially.The size of prepared oxidation film integrity degree and oxide particle, and the factors such as concentration of oxide colloid deposit fluid are directly related.The oxide particle that uses is more little, and the oxide coating that obtains on woven wire is even more, densification.For example, sample A
14Can perfectly preserve through this oxidation film structure after the calcination process, handle, do not find coming off of oxidation film through ultrasonic wave.In the diffraction pattern of oxidation film except the diffraction maximum at the stainless steel-based end, Detitanium-ore-type TiO has appearred also
2Characteristic peak.This has proved through after the electrostatic precipitation, TiO
2Particle has deposited on the stainless steel steel wire.This method also has the advantage of universality, can prepare various types of oxide nets on the net in various Metal Substrate, and by alternately adsorbing the oxidation film that different types of oxide colloid can also obtain heterozygosis.
Claims (11)
1. method for preparing metal base nano oxide net, it is characterized in that the glue of nano-oxide as the absorption deposit fluid, wire netting is as matrix, utilize the electrostatic attraction between nano-oxide and the polyelectrolyte, nano-oxide is deposited on the woven wire matrix in the layer laminate mode, and actual conditions is:
(1) the nano-oxide gelatin concentration is 0.05～20%wt%;
(2) wire netting surface preparation: wire netting was soaked 5 minutes～1 hour at the polycation electrolyte solution of concentration 0.1-5%, clean, soaked 5 minutes～1 hour with 0.1～5% polyanion electrolyte solution again, circulate repeatedly;
(3) wire netting that the surface is charged gelatin concentration be 0.05～20wt%, pH be soak in 1～14 the oxide glue, washing, alternately adsorb polyelectrolyte and oxide colloid and dry, per step sedimentation time 1 second～20 hours dries 5～200 ℃ of temperature;
(4) product dries or 200～1000 ℃ of following roastings in the atmosphere of nitrogen or other inertia 1～50 hour time at 5～200 ℃.
2. a kind of method for preparing metal base nano oxide net according to claim 1 is characterized in that the nano-oxide crystallite dimension is 1～5000 nanometer.
3. a kind of method for preparing metal base nano oxide net according to claim 1 is characterized in that the gelatin concentration that nano-oxide disperses is 0.1～10%.
4. a kind of method for preparing metal base nano oxide net according to claim 1 is characterized in that the pH value of nano oxidized composition glue liquid is 2～12.
5. a kind of method for preparing metal base nano oxide net according to claim 1 is characterized in that poly-dielectric is polycation dielectric or polyanion dielectric.
6. a kind of method for preparing metal base nano oxide net according to claim 1 is characterized in that adsorbing the product that obtains after the deposition and dries at 40～160 ℃.
7. a kind of method for preparing metal base nano oxide net according to claim 1, it is characterized in that sintering temperature is 400～800 ℃, in not corroding woven wire matrix gas atmosphere, kept 0～12 hour, perhaps kept in oxygen or the air 1～8 hour.
8. a kind of method for preparing metal base nano oxide net according to claim 2 is characterized in that the oxide colloid size is 1～200 nanometer.
9. a kind of method for preparing metal base nano oxide net according to claim 1 is characterized in that this method is applicable to copper mesh, steel mesh, nickel screen.
10. a kind of method for preparing metal base nano oxide net according to claim 1 is characterized in that this method can be used to prepare Metal Substrate composite nano oxide net.
11. a kind of method for preparing metal base nano oxide net according to claim 1 is characterized in that woven wire is a stainless (steel) wire.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01126993 CN1124897C (en) | 2001-10-11 | 2001-10-11 | Method for preparing metal base nano oxide net |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01126993 CN1124897C (en) | 2001-10-11 | 2001-10-11 | Method for preparing metal base nano oxide net |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1354048A CN1354048A (en) | 2002-06-19 |
| CN1124897C true CN1124897C (en) | 2003-10-22 |
Family
ID=4666994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01126993 Expired - Fee Related CN1124897C (en) | 2001-10-11 | 2001-10-11 | Method for preparing metal base nano oxide net |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1124897C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7354850B2 (en) * | 2004-02-06 | 2008-04-08 | Qunano Ab | Directionally controlled growth of nanowhiskers |
| US8623779B2 (en) * | 2011-02-04 | 2014-01-07 | Ford Global Technologies, Llc | Catalyst layer supported on substrate hairs of metal oxides |
| CN105986480B (en) * | 2015-02-13 | 2019-06-28 | 清华大学 | Protective coating, filtrate, matrix and its protective coating preparation method |
| CN109647052A (en) * | 2018-12-04 | 2019-04-19 | 山西绿建科技有限公司 | A kind of preparation method of antibacterial air conditioner filter element material |
| CN113144752A (en) * | 2021-04-30 | 2021-07-23 | 安阳振动器有限责任公司 | Preparation method of special composite filter screen for air purification of train carriage |
| CN115770561B (en) * | 2022-10-20 | 2023-06-02 | 西北民族大学 | Preparation and application of pulse dip-coating type micro-channel nano catalyst coating |
-
2001
- 2001-10-11 CN CN 01126993 patent/CN1124897C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1354048A (en) | 2002-06-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3617146B1 (en) | Linear porous titanium dioxide material and preparation and use thereof | |
| US11465129B2 (en) | Microwave assisted and low-temperature fabrication of nanowire arrays on scalable 2D and 3D substrates | |
| Zhao et al. | From solid-state metal alkoxides to nanostructured oxides: a precursor-directed synthetic route to functional inorganic nanomaterials | |
| CN105363483A (en) | Preparation method of titanium dioxide nanowire/two-dimensional layered titanium carbide composite material | |
| JP2007519165A (en) | Nanostructured metal-carbon composite for electrode catalyst of fuel cell and production method thereof | |
| Han et al. | Research progresses in the preparation of Co-based catalyst derived from Co-MOFs and application in the catalytic oxidation reaction | |
| CN1608727A (en) | Supported TiO2 photocatalyst and its prepn process | |
| Chen et al. | Boosted charge transfer and photocatalytic CO2 reduction over sulfur-doped C3N4 porous nanosheets with embedded SnS2-SnO2 nanojunctions | |
| CN113908866A (en) | Titanium carbide composite material loaded with cobalt-containing compound and preparation method and application thereof | |
| CN1802208A (en) | Catalyst for fuel cell oxygen electrodes | |
| Li et al. | Transition metal Carbides/Nitrides (MXenes): Characteristics, synthesis, functional modification and photocatalytic application | |
| CN1124897C (en) | Method for preparing metal base nano oxide net | |
| Zhang et al. | Raspberry-like TiO 2 hollow spheres consisting of small nanocrystals towards efficient NO removal | |
| Kai et al. | In situ growth of CdS spherical nanoparticles/Ti 3 C 2 MXene nanosheet heterojunction with enhanced photocatalytic hydrogen evolution | |
| Peng et al. | RETRACTED: Atomic layer deposition of Pt nanoparticles on ZrO2 based metal-organic frameworks for increased photocatalytic activity | |
| Quan et al. | Superior performance in visible-light-driven hydrogen evolution reaction of three-dimensionally ordered macroporous SrTiO 3 decorated with Zn x Cd 1− x S | |
| CN1142014C (en) | Method of loading titanium dioxide photo catalyst on metal surface | |
| Lu et al. | Ion-exchange loading promoted stability of platinum catalysts supported on layered protonated titanate-derived titania nanoarrays | |
| CN112495403B (en) | BiOCl/Bi 2 O 3 Photocatalytic material and preparation method and application thereof | |
| CN1887416A (en) | Microwave process and application of foamed nickel supported and modified nanometer TiO2 | |
| CN110180542B (en) | Titanium dioxide/graphene/metal simple substance ternary composite photocatalytic material and photoreduction preparation method | |
| CN114164446B (en) | Cu doped CeO derived from metal organic framework 2 PdCu alloy loaded catalyst and preparation method thereof | |
| Zhang | Current diatom research in China | |
| CN114496586A (en) | Nitrogen-doped three-dimensional graphene/MOF (Metal organic framework) derived carbon composite electrode material for capacitive deionization and preparation and application thereof | |
| CN113215609A (en) | Preparation of silver nanocluster sensitized titanium dioxide composite photo-anode for photoelectrocatalysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |